Positioning the reference electrode in proton exchange membrane fuel cells: calculations of primary and secondary current distribution

The primary and secondary current distribution study indicates the geometry of a thin electrolyte in a proton exchange membrane (PEM) fuel cell has a direct relation to the measured electrode polarization, thus making the positioning of the reference electrode and ohmic compensation critical. The different kinetic overpotentials on the electrodes can also affect the potential distribution and therefore affect the measurement accuracy. The measurement error can be significant for the fuel cell system with different kinetic overpotentials and with electrode misalignment. The measurement error for both hydrogen and direct methanol fuel cells (DMFC) has been analyzed over the current density region with no mass transfer effects. By using two reference electrodes, the measurement error can be substantially decreased for both anode and cathode measurement in a direct methanol fuel cell, and for the cathode measurement in a hydrogen/air fuel cell.     

The effect of methanol and ethanol cross-over on the performance of PtRu/C-based anode DAFCs

In the present work, the cross-over rates of methanol and ethanol, respectively, through Nafion^®-115 membranes at different temperatures and different concentrations have been measured and compared. The changes of Nafion^®-115 membrane porosity in the presence of methanol or ethanol aqueous solutions were also determined by weighing vacuum-dried and alcohol solution-equilibrated membranes. The techniques of anode polarization and adsorption stripping voltammetry were applied to compare the electrochemical activity and adsorption ability, respectively. To investigate the consequences of methanol and ethanol permeation from the anode to the cathode on the performance of direct alcohol fuel cells (DAFCs), single DAFC tests, with methanol or ethanol as the fuel, have been carried out and the corresponding anode and cathode polarizations versus dynamic hydrogen electrode (DHE) were also performed. The effect of alcohol concentration on the performance of PtRu/C anode-based DAFCs was investigated.It was found that ethanol shows lower cross-over rates than methanol through the Nafion^® membrane in spite of the higher membrane porosity resulted in presence of ethanol aqueous solutions. Furthermore, it was found that ethanol presents less negative effect on the cathode performance due to both its smaller permeability through Nafion^® membrane and its slower electrochemical oxidation kinetics over Pt/C cathode.     

Carbon supported and unsupported Pt–Ru anodes for liquid feed direct methanol fuel cells

A comparative study of the use of supported and unsupported catalysts for direct methanol fuel cells has been performed. The effect of catalyst loading, fuel concentration and temperature dependence on the anode, cathode and full fuel cell performance was determined in a fuel cell equipped with a reversible hydrogen reference electrode. Although the measured specific activities of supported catalysts were as much as 3-fold greater than the unsupported catalysts, membrane electrode assemblies prepared with supported catalysts showed no improvement with loadings above 0.5 mg/cm². Fuel cells utilizing 0.46 mg/cm² supported catalyst electrodes performed as well as unsupported catalyst electrodes with 2 mg/cm². The temperature dependence and methanol concentration dependence studies both suggest increased methanol permeation through the thinner supported catalyst layers relative to the unsupported catalyst layers.     

An experimental study on the placement of reference electrodes in alkaline polymer electrolyte membrane fuel cells

The ability to accurately measure separate in situ anode and cathode overpotentials and impedance responses is still a source of debate when investigating fuel cells of planar configuration containing <100 μm thickness solid electrolytes and when using the common three-electrode arrangement. The results obtained in this study indicate that the overpotentials and impedances of the anode and cathode can be successfully measured when using two spatially separated reference electrodes and when the cathode and anode of alkaline membrane electrode assemblies (for alkaline polymer electrolyte membrane fuel cells) are precisely and optimally misaligned. The frequency dependent response between the two reference electrodes is attributed to the membrane response and the “crosstalk” between anode and cathode.     

Methanol crossover effect on the cathode potential of a direct PEM fuel cell

The potential of the oxygen cathode in a direct methanol fuel cell is strongly influenced by the crossover of methanol through the poly-electrolyte membrane. In the presence of methanol, oxygen is reduced at the cathode already at open circuit and the equivalent amount of methanol is oxidized. This results in the formation of a mixed potential, up to 200 mV negative to the original oxygen potential. In this work, the anode and cathode potentials of a DMFC are monitored in situ, using a dynamic hydrogen electrode (DHE). For the first time, the effect of crossover on the cathode potential as function of time is presented. Methanol and ethanol as fuels are compared. Changing from methanol to hydrogen, the influence of methanol crossover on the cathode potential can also be followed as function of current density. It is already known that, in addition to the consumption of fuel and oxygen with the formation of a mixed potential, a purely chemical reaction takes place at the platinum surface. A quantitative determination of the respective CO₂ formation is presented here.     

Role of hydrophobic anode MPL in controlling water crossover in DMFC

The importance of reducing water crossover from anode to cathode in a direct methanol fuel cell (DMFC) has been well documented, especially if highly concentrated methanol fuel is to be used. A low-α membrane electrode assembly (MEA) with thin membrane is key to achieving this goal. The low water crossover from anode to cathode for these types of MEAs has traditionally been attributed to the use of a hydrophobic cathode micro-porous layer (MPL). However, it has recently been discovered that a hydrophobic anode MPL also reduces the water crossover, possibly even more significantly than a hydrophobic cathode MPL. In this work, we develop and use a 1D, two-phase transport model that accounts for capillary-induced liquid flow in porous media to explain how a hydrophobic anode MPL controls the water crossover from anode to cathode. We further show that a lower water crossover can lead to a lower methanol crossover via dilution of methanol in the anode catalyst layer. Finally, we perform a parametric study and show that a thicker anode MPL with greater hydrophobicity and lower permeability is more effective in reducing the water crossover.     

Design of a reference electrode for high-temperature PEM fuel cells

In this work, we present the design of an external reference electrode for high-temperature PEM fuel cells. The connection between the reference electrode with one of the fuel cell electrodes is realized by an ionic connector. Using the same material for the ionic connection as for the fuel cell membrane gives us the advantage to reach temperatures above 100 °C without destroying the reference electrode. This configuration allows for the separation of the anode and cathode overpotential in a working fuel cell system. In addition to the electrode overpotentials in normal hydrogen/air operation, the influence of CO and CO + H₂O in the anode feed on the fuel cell potentials was investigated. When CO poisons the anode catalyst, not only the anode potential increased, but also the cathode overpotential, due to fewer protons reaching the cathode. By the use of synthetic reformate containing hydrogen, carbon monoxide and water on the anode, fuel cell voltage oscillations were observed at high constant current densities. The reference electrode measurements showed that the fuel cell oscillations were only related to reactions on the anode side influencing the anode overpotential. The cathode potential, in contrast, was only negligibly affected by the oscillations under the applied conditions.     

PEM fuel cell Pt anode inhibition by carbon monoxide: Non-uniform behaviour of the cell caused by the finite hydrogen excess

Inhibition of platinum surfaces by carbon monoxide, in particular in polymer membrane electrolyte fuel cells (PEMFC) has been observed for decades by electrochemists. Significant effects have been observed in the hydrogen stream fed to the anode of the fuel cell with concentrations ranging from 1 to 100 ppm depending on the operating conditions e.g. temperature, pressure and excess in reacting gases. As a matter of fact, the gas composition and the surface coverage by CO and H₂ vary in the cell, because of the hydrogen consumption at the anode: this is to result to non-uniform distributions of electrode poisoning, current density, and overvoltage, from the inlet to the outlet of the cell. A simple 1D-model has been developed for prediction of the profiles of the above variables in the fuel cells, with the support of experimental data obtained with a 25 cm² PEMFC: interpretation of polarization curves and impedance spectra yielded the kinetic laws of the two electrode reactions, with both neat hydrogen and CO-containing hydrogen at ppm levels. Simulations show that for low excess in hydrogen – as for practical use of fuel cells – the coverage fractions of the various species can greatly vary in the cell, resulting in non-uniform distributions of current density in the cell and enhanced electrode poisoning near the cell outlet. In contrast working with very high hydrogen excess, as can be done at bench scale, leads to uniform behaviour of the cell, and far less visibility of the anode poisoning by carbon monoxide.     

Effect of Hot Pressing on the Performance of Direct Methanol Fuel Cells

The effects of hot pressing of electrodes onto Nafion^® membranes in the preparation of membrane and electrode assemblies for direct methanol fuel cells have been investigated. Hot pressing does not significantly influence the cell resistance or methanol crossover, but it can decrease cell performance by restricting mass transport in the anode catalyst layer. It also increases the time required for the cell to reach optimum performance. Best performances were obtained with membrane and electrode assemblies that had not been pressed. It was also found that membranes that had not been subjected to hot pressing could easily be re-used, making recycling of membranes and catalysts more feasible.     

Current Status of and Recent Developments in the Direct Methanol Fuel Cell

The direct methanol fuel cell (DMFC) has been discussed recently as an interesting option for a fuel‐cell‐based mobile power supply system in the power range from a few watts to several hundred kilowatts. In contrast to the favoured hydrogen‐fed fuel cell systems (e.g. the polymer electrolyte membrane fuel cell, PEMFC), the DMFC has some significant advantages. It uses a fuel which is, compared to hydrogen, easy to handle and to distribute. It also comprises a fairly simple system design compared to systems utilising liquid fuels (like methanol) to produce hydrogen from them by steam reforming or partial oxidation to finally feed a standard PEMFC. Nevertheless, many severe problems still exist for the DMFC, hindering its competitiveness as an option to hydrogen‐fed fuel cells. This work reviews the major research activities concerned with the DMFC by highlighting the problems (slow kinetics of the anodic methanol oxidation, methanol permeation through the membrane, carbon dioxide evolution at the anode) and their possible solutions. Special attention is devoted to the steady state and dynamic simulation of these fuel cell systems.     

Li–H<Subscript>2</Subscript> cells with molten alkali chlorides electrolyte

Li–H₂ thermally regenerative fuel cells were studied using molten alkali chlorides as the electrolyte at relatively lower temperature. The saturation solubility of LiH in three different alkali chloride eutectic melts (LiCl–KCl, LiCl–CsCl, and LiCl–KCl–CsCl) was determined based on equilibrium potential measurements for the hydrogen electrode. Both a Ni membrane electrode and porous Ni electrode were evaluated as the cathode of the cell. In addition, a single cell of a Li–H₂ fuel cell with a Ni membrane for the anode was constructed, and the electromotive force (emf) was measured. When the Ni membrane electrode performed as an anode with molten salt electrolyte saturated with LiH, the measured emf was similar to previously reported emf for other types of molten salt electrolyte. In conclusion, certain types of molten alkali chlorides can be used as the electrolyte of a thermally regenerative fuel cell at a relatively lower operating temperature at least above 598 K.     

Direct methanol alkaline fuel cells with catalysed anion exchange membrane electrodes

Membrane electrodes prepared by chemical deposition of platinum directly onto the anion exchange membrane electrolyte were tested in direct methanol alkaline fuel cells. Data on the cell voltage against current density performance and anode potentials are reported. The relatively low fuel cell performance was probably due to the low active surface area of Pt deposits on the membrane comparing to other membrane electrode assembly (MEA) fabrication methods. However, the catalysed membrane electrode showed good performance for oxygen reduction. A reduction in cell internal resistance was also obtained for the catalysed membrane electrode. By combining the catalysed membrane electrodes with a catalysed mesh, maximum current density of 98 mA cm^–2 and peak power density of 18 mW cm^–2 were achieved.     

Methanol oxidation at carbon supported Pt and Pt-Ru electrodes: an on line MS study using technical electrodes

Methanol oxidation at technical carbon based electrodes in 0.05 M H₂SO₄ has been investigated by cyclic voltammetry using online MS under the conditions of an acid methanol fuel cell (DMFC). 5% Pt on Norit BRX and 30% Pt/Ru (40/60) on Norit BRX were used as catalysts. It is shown that methanol oxidation at technical electrodes can be characterized by a combination of cyclic voltammetry and mass spectroscopy. The onset potentials and potential dependences of the methanol oxidation rate can be determined directly by monitoring the formation of CO₂. Onset potentials of 0.5V and 0.25 V/RHE have been measured for Pt and Pt-Ru catalysts, respectively. The onset of methanol oxidation can be shifted to even more cathodic potentials (0.2V) if the Pt-Ru electrode reduces oxygen simultaneously. Carbon monoxide gas was also purged into the methanol containing electroyte during measurement in order to investigate the catalyst performance under more adverse conditions. C¹³-labelled methanol was used to distinguish between CO₂. formed from methanol (m/e = 45) and CO-oxidation (m/e = 44). Without CO the use of C¹³-labelled methanol enabled a distinction between methanol oxidation and carbon corrosion. The methanol oxidation at the platinum catalyst is severely inhibited by the presence of CO, shifting its onset to 0.65 V/RHE. In contrast the performance of the Pt-Ru electrode is not seriously affected under these conditions. It is concluded that Pt-Ru is an excellent catalyst for a methanol anode in an acid methanol fuel cell (DMFC).     

Aspects of the anodic oxidation of methanol

This paper describes some aspects of recent investigations into the anodic oxidation of methanol. Methanol has long been proposed as an anode fuel for a fuel cell, chiefly because of its ease of carriage, distribution and manipulation. However, methanol is very much more difficult to oxidise anodically than hydrogen, the more conventional anode fuel, and this has hampered development of commercial direct methanol fuel cells. Platinum-ruthenium catalysts are the most active discovered to date. Some advances in electrocatalysis of the methanol reaction by non-noble materials are discussed.     

First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide

The strong drive to commercialize fuel cells for portable as well as transportation power sources has led to the tremendous growth in fundamental research aimed at elucidating the catalytic paths and kinetics that govern the electrode performance of proton exchange membrane (PEM) fuel cells. Advances in theory over the past decade coupled with the exponential increases in computational speed and memory have enabled theory to become an invaluable partner in elucidating the surface chemistry that controls different catalytic systems. Despite the significant advances in modeling vapor-phase catalytic systems, the widespread use of first principle theoretical calculations in the analysis of electrocatalytic systems has been rather limited due to the complex electrochemical environment. Herein, we describe the development and application of a first-principles-based approach termed the double reference method that can be used to simulate chemistry at an electrified interface. The simulations mimic the half-cell analysis that is currently used to evaluate electrochemical systems experimentally where the potential is set via an external potentiostat. We use this approach to simulate the potential dependence of elementary reaction energies and activation barriers for different electrocatalytic reactions important for the anode of the direct methanol fuel cell. More specifically we examine the potential-dependence for the activation of water and the oxidation of methanol and CO over model Pt and Pt alloy surfaces. The insights from these model systems are subsequently used to test alternative compositions for the development of improved catalytic materials for the anode of the direct methanol fuel cell.     

Cobalt-polypyrrole-multiwalled carbon nanotube catalysts for hydrogen and alcohol fuel cells

A cobalt-polymer-MWCNT composite has been developed as an electrocatalyst for the oxygen reduction reaction (ORR) in PEMFC. The suitability of this electrocatalyst for the ORR in direct methanol fuel cells and direct ethanol fuel cells has been examined by taking Pt-Ru/MWCNT and Pt-Sn/MWCNT, respectively as an anode electrocatalysts. The study results in improved power densities for hydrogen, methanol and ethanol based fuel cells compared to the previously reported non Pt based electrocatalysts, highlighting the use of this cobalt-polymer-MWCNT composite as a potential candidate for ORR in fuel cells.     

Carbon aerogel supported Pt-Ru catalysts for using as the anode of direct methanol fuel cells

A carbon aerogel (CA) loaded with platinum nanoparticles can achieve good catalytic performance in proton exchange membrane fuel cells. Pt-Ru bimetallic nanoparticles were loaded onto a carbon aerogel through a simple process. The PtRu/CA achieved good cell performance when used as a direct methanol fuel cell anode catalyst. The advantages of carbon aerogel may be attributed to the mesopore structure that can facilitate the mass transportation in the electrode. The Ru content in the catalyst has a great influence on its performance. The PtRu/CA with 25 at.% Ru achieves the best cell performance at 30 °C.     

Direct Methanol Fuel Cells Using Thermally Catalysed Ti Mesh

Characterisation of a direct methanol fuel cell using an anode fabricated by thermal decomposition from Pt–Ru chloro-complex on Ti mesh is described. The polarisation characteristic of the resultant membrane electrode assembly is compared with that of a conventional MEA with an anode, consisting of a catalyst layer, a microporous layer and a wet-proof-treated carbon paper. Electrode characterisation was carried out using XRD, SEM and EDX analyses. In 1 m methanol solution, the MEA with the catalysed Ti mesh anode gave a power performance comparable with that of the conventional anode at 90 °C. However, in 0.5 m methanol solution the former showed much higher power density than the latter, indicating high utilisation of methanol fuel.     

Investigation of fuel and media flexible laminar flow-based fuel cells

We investigate the performance of air-breathing laminar flow-based fuel cells (LFFCs) operated with five different fuels (formic acid, methanol, ethanol, hydrazine, and sodium borohydride) in either acidic or alkaline media. The membraneless LFFC architecture enables interchangeable operation with different fuel and media combinations that are only limited by the actual anode catalyst used. Furthermore, operating under alkaline conditions significantly improves methanol and ethanol oxidation kinetics and stabilizes sodium borohydride. LFFCs operated with hydrazine and sodium borohydride as fuels exhibit power densities of 80 and 101 mW/cm², respectively. To optimize anode performance, particularly for ethanol electro-oxidation, we introduced a hydrogen cathode to the membraneless LFFC design which renders the cell an ideal platform for anode investigation. Here, we highlight two simple diagnostic methods, in situ single electrode studies and electrochemical impedance spectroscopy (EIS), for characterizing and optimizing the performance of a direct ethanol LFFC anode.     

Accelerated durability test of DMFC electrodes by electrochemical potential cycling

Durability of direct methanol fuel cell electrodes was evaluated by electrochemical potential cycling and we observed the degradation phenomena during the performance decay. An individual potential measurement of anode and cathode with built-in reversible hydrogen electrode revealed that the anode and cathode performance contributions are almost of the same order of magnitude to the entire performance loss, although the anode degradation is relatively bigger, due to the dominating effect of ruthenium dissolution, corresponding loss of electrocatalytic activity. On the contrary, it was apparent that the electrochemical active surface area of Pt cathode decreased significantly with potential cycling under methanol crossover condition, which is not clearly reflected on the performance loss due to the initial decrease of interfacial resistance between membrane and cathode catalyst layer. Impedance studies could reinforce the current–voltage polarization by more comprehensive information.